Nitrile and aldoxime indane compounds and compositions

ABSTRACT

The present invention relates to novel nitrile and aldoxime indane compounds, such as 1,1,2,3,3,4,6-heptamethylindane-5-nitrile and 1,1,2,3,3,4,6-heptamethylindane-5-aldoxime, and to compositions containing the same. Compounds and compositions of the invention possess a fragrant musk-like aroma, and thus are useful in the perfumery and/or other industries.

BACKGROUND OF THE INVENTION

The present invention relates to novel nitrile and aldoxime indanecompounds and compositions having a fragrant musk-like aroma, and toprocesses for their preparation.

Musk fragrances are in great demand for use in various products such asin perfumes, colognes, cosmetics, soaps and others. However, naturalmusk, which is obtained from the Asian musk deer, is extremely scarceand is quite expensive. Accordingly, fragrance chemists have spentconsiderable time searching for synthetic products which duplicate orclosely simulate this natural musk scent.

As a result of these research efforts, a number of different syntheticmusks have been discovered. Among such synthetic compounds are theacetyl indanes described by U.S. Pat. No. 4,466,908, compounds of theformulas ##STR1## which may be employed, if desired, in combination withacetyl tetrahydronaphthalenes of the formula ##STR2## Similarly, Fehr etal., Helvetica Chimica Acta, Vol. 72, pp. 1537-1553 (1989) discussessuch synthetic musks as those of the formula ##STR3## wherein R iseither H or CH₃.

U.S. Pat. No. 4,352,748 discloses formylated and acetylated indanemusks, including those of the formulas ##STR4##

Other acetyl indanes, such as 6-acetyl-1,1,3,3,5-pentamethylindane,5-acetyl-1,1,2,3,3-pentamethylindane and6-acetyl-5-ethyl-1,1,2,3,3-pentamethylindane, are disclosed in FrenchPatent No. 1,392,804 (as reported in Chemical Abstracts, Vol. 63, p.1681d (1965)).

European Patent Publication 0 301 375 A2 describes formylated tetralins,such as 1,1,2,4,4-pentamethyl-6-formyl-1,2,3,4-tetrahydronaphthalene,and their utility as synthetic musks.

Certain synthetic nitrile indane and tetralin compounds having muskaroma properties have also been described in the literature. Forexample, De Simone, U.S. Pat. No. 4,018,719, discusses the nitrileindane musk compound 1,1,2,3,3,5-hexamethylindane-6-nitrile, a compoundof the formula ##STR5## Christenson et al., U.S. Pat. No. 4,483,786describes the nitrile tetralin musk compounds1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-carbonitrileand3-ethyl-1-methoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene-2-carbonitrile.Similarly, Kulka, U.S. Pat. No. 3,910,853 discusses1,1,4,4-tetramethyl-alkyl-nitrile-tetrahydronaphthalene musk perfumecompositions. Christenson et al., U.S. Pat. No. 4,483,786 and Kulka,U.S. Pat. No. 3,910,853 also describe processes for the preparation ofnitrile compounds involving oximation and oxime dehydration.

New and/or better musk aroma compounds are needed. The present inventionis directed to this as well as other important ends.

SUMMARY OF THE INVENTION

The present invention provides novel compounds of the formula [I]:##STR6## wherein R¹ is H, CH₃, and CH₂ CH₃, and

R² is CH₃, and CH₂ CH₃.

The subject invention also provides novel compositions comprising, incombination, at least two compounds of formula [I].

The present invention is also directed to novel compounds of the formula[II]: ##STR7## wherein R¹ is H, CH₃, and CH₂ CH₃, and

R² is CH₃, and CH₂ CH₃.

The subject invention also provides novel compositions comprising, incombination, at least two compounds of formula [II].

The foregoing formula [I] and [II] compounds and compositions possessactive musk aroma fragrances having utility in the perfumery and/orother industries. The compounds and compositions of the invention can beused alone or in combination with other compounds or ingredients, andthus the present invention is further directed to the use of compoundsand compositions of formulas [I] and/or [II] in combination withcarriers and/or additional perfumery ingredients as fragrancecompositions.

DETAILED DESCRIPTION OF THE INVENTION

As noted above, the present invention is directed to novel muskcompounds of the formula [I]: ##STR8## wherein R¹ is H, CH₃, and CH₂CH₃, and

R² is CH₃, and CH₂ CH₃.

Preferably the formula [I] compounds are those compound wherein:

R¹ is CH₃, and R² is CH₃, a compound which is1,1,2,3,3,4,6-heptamethylindane-5-nitrile;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located cis to oneanother (that is, on the same side of the indane ring plane), a compoundwhich is cis-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located trans to oneanother (that is, on the opposite side of the indane ring plane), acompound which is trans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile;

R¹ is H, and R² is CH₃, a compound which is1,1,3,3,4,6-hexamethylindane-5-nitrile; and

R¹ is H, R² is CH₂ CH₃, a compound which is3-ethyl-1,1,3,4,6-pentamethylindane-5-nitrile.

The most preferred formula [I] compound is1,1,2,3,3,4,6-heptamethylindane-5-nitrile, a compound of the formula:##STR9##

The formula [I] compounds or compositions may be employed alone, or incombination with one another, as compositions useful in the perfumery orother industries. A particularly preferred composition is onecomprising, in combination, formula [I] compounds which are1,1,2,3,3,4,6-heptamethylindane-5-nitrile,cis-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile,trans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile,1,1,3,3,4,6-hexamethylindane-5-nitrile, and3-ethyl-1,1,3,4,6-pentamethylindane-5-nitrile.

As noted above, the present invention is also directed to novel muskcompounds of formula [II]: ##STR10## wherein R¹ is H, CH₃, and CH₂ CH₃,and

R² is CH₃, and CH₂ CH₃.

Preferably the formula [II] compounds are those compound wherein:

R¹ is CH₃, and R² is CH₃, a compound which is1,1,2,3,3,4,6-heptamethylindane-5-aldoxime;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located cis to oneanother (that is, on the same side of the indane ring plane), a compoundwhich is cis-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-aldoxime;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located trans to oneanother (that is, on the opposite side of the indane ring plane), acompound which is trans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-aldoxime;

R¹ is H, and R² is CH₃, a compound which is1,1,3,3,4,6-hexamethylindane-5-aldoxime; and

R¹ is H, R² is CH₂ CH₃, a compound which is3-ethyl-1,1,3,4,6-pentamethylindane-5-aldoxime.

The most preferred formula [II] compound is1,1,2,3,3,4,6-heptamethylindane-5-aldoxime.

The formula [II] compounds or compositions may be employed alone, or incombination with one another, as compositions useful in the perfumery orother industries. A particularly preferred composition is onecomprising, in combination, formula [II] compounds which are1,1,2,3,3,4,6-heptamethylindane-5-aldoxime,cis-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-aldoxime,trans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-aldoxime,1,1,3,3,4,6-hexamethylindane-5-aldoxime, and3-ethyl-1,1,3,4,6-pentamethylindane-5-aldoxime.

The novel indane compounds and compositions of the invention can beprepared in various fashions. In the preferable protocol, compounds ofthe formula [IV] ##STR11## wherein R¹ is H, CH₃, and CH₂ CH₃, and

R² is CH₃, and CH₂ CH₃,

are first prepared, and are then formylated, to yield the compounds offormula [III]: ##STR12## wherein R¹ is H, CH₃, and CH₂ CH₃,

R² is CH₃, and CH₂ CH₃, and

R³ is CHO.

Preferably, the formula [III] compounds are then converted to thealdoxime compounds of formula [II] by employing standard oximationtechniques, and the formula [II] compounds are then converted to thenitrile compounds of formula [I] using conventional oxime dehydrationmethodology.

In accordance with one preferable protocol, the compounds of formula[IV] are prepared by contacting a compound selected from the groupconsisting of 5-isopropyl-meta-xylene and 5-isopropenyl-meta-xylene,with a compound selected from the group consisting of 2-methyl-2-butene,2-methylpropene (also referred to as isobutylene), 2-methyl-1-butene,3-methyl-2-pentane, 2-methyl-2-pentane, and 3-methyl-3-hexene. Inanother preferable process, the compound of formula [IV] wherein R¹ andR² are both CH₃ is prepared by contacting metaxylene with2,4-dichloro-2,3,4-trimethylpentane. The foregoing reactants can besynthesized using conventional organic synthesis procedures and/orpurchased from various commercial sources. For example, a productcontaining 98% 2-methyl-2-butene is sold by Aldrich Chemical Company,Milwaukee, Wis., under the trademark Isoamylene™. In carrying out theforegoing processes, the reactants are combined with a Lewis acid or aprotonic acid, a solvent which can be a halogenated or unhalogenatedsolvent, and optionally, a phase transfer agent, to form the compoundsof formula [IV]. As those skilled in the art would recognize, a Lewisacid can be employed with any of the reactants, while the protonic acidis employed only with those reactions involving the reactant5-isopropenyl-meta-xylene.

Any of the Lewis acids, that is, any non-protonic compounds capable ofaccepting an electron pair, are suitable for use in the foregoingprocesses. Exemplary Lewis acids include metal halides such as aluminumhalides, including aluminum chloride, aluminum bromide, aluminum iodide,monofluorodichloroaluminum, monobromodichloroaluminum andmonoiododichloroaluminum. Alkyl metals and alkyl metal halides suitablefor use as Lewis acids in the present processes are disclosed, forexample, in Kennedy, Joseph P., Carbocationic Polymerization, p. 221(Wiley-Interscience Publishers, 1982), the disclosures of which areincorporated herein by reference. In the subject processes, aluminumhalides are preferred. Of the aluminum halides, aluminum chloride andaluminum bromide, particularly aluminum chloride (AlCl₃), are mostpreferred.

Any of the protonic acids are suitable for use with the foregoingprocesses involving the reactant 5-isopropenyl-meta-xylene. Exemplaryprotonic acids include sulfuric acid, phosphoric acid, methane sulfonicacid, para-toluene sulfonic acid, and the like.

Halogenated solvents suitable for use in the processes are varied, andinclude halogenated aliphatic, halogenated alicyclic and halogenatedaromatic hydrocarbon solvents. Particularly preferred are thehalogenated aliphatic hydrocarbons. Suitable halogenated solventsinclude, for example, 1,2-dichloroethane, 1,1-dichloroethane,trichloromethane, dichloromethane, 1,1,2,2-tetrachloroethylene,1,2-dichloroethylene, 1,2,3-trichloropropane, 1,1,2-trichloroethane,monochlorobenzene, fluorobenzene, and orthodichlorobenzene. Particularlypreferred halogenated solvents include dichloromethane, trichloromethaneand 1,2-dichloroethane.

As an alternative to or in combination with halogenated solvents, onemay employ unhalogenated solvents. A variety of unhalogenated solventsmay be utilized, including, unhalogenated aliphatic, unhalogenatedalicyclic and unhalogenated aromatic hydrocarbon solvents. Suchunhalogenated solvents are generally preferred over the halogenatedsolvents for reasons of safety. Particularly preferred are theunhalogenated aliphatic and unhalogenated alicyclic hydrocarbons.Suitable unhalogenated solvents include, for example, the aliphatichydrocarbon solvents n-hexane, n-heptane and n-octane, the alicyclichydrocarbon solvent cyclohexane, and the aromatic hydrocarbon solventsbenzene, and mesitylene (1,3,5-trimethyl-benzene). A particularlypreferred unhalogenated solvent is the unhalogenated alicyclichydrocarbon solvent cyclohexane.

Phase transfer agents suitable for use in the processes include oniumsalts such as ammonium, phosphonium and sulfonium salts. Other phasetransfer agents suitable for use in the present processes will bereadily apparent to those skilled in the art, once having been madeaware of the present disclosure.

Examples of ammonium phase transfer agents include quaternary ammoniumhalides such as methyltrioctylammonium chloride, methyltrinonylammoniumchloride, methyltridecylammonium chloride, hexadecyltrihexylammoniumbromide, ethyltrioctylammonium bromide, didodecyldimethylammoniumchloride, tetraheptylammonium iodide, dioctadecyldimethylammoniumchloride, tridecylbenzylammonium chloride, ditricosylmethylammoniumchloride, and homologues thereof having chlorine, fluorine, bromine oriodine atoms substituted for the enumerated halide atom.

Exemplary phosphonium phase transfer agents include quaternaryphosphonium halides such as tributyldecylphosphonium iodide,triphenyldecylphosphonium iodide, tributylhexadecylphosphonium iodide,and homologues thereof having chlorine, fluorine or bromine atomssubstituted for the iodine atom.

Representative sulfonium phase transfer agents include ternary sulfoniumhalides such as lauryldimethylsulfonium iodide, lauryldiethylsulfoniumiodide and tri(n-butyl)sulfonium iodide, and homologues thereof havingchlorine, fluorine or bromine atoms substituted for the iodine atom.

These and other suitable phase transfer agents are described, forexample, in Napier et al., U.S. Pat. No. 3,992,432 entitled "PhaseTransfer Catalysis of Heterogenous Reactions by Quaternary Salts", andin Kondo et al., Synthesis, pp. 403-404 (May 1988), the disclosures ofwhich are incorporated herein by reference.

Preferable phase transfer agents are ammonium or sulfonium salts,particularly quaternary ammonium or ternary sulfonium halides. Mostpreferred are quaternary ammonium halides, particularlymethyltrioctylammonium chloride, and a mixture of methyltrioctylammoniumchloride and methyltridecylammonium chloride. The latter mixture ismarketed under the trademark Adogen-464™, by Sherex Co., located inDublin, Oh.

In general, the molar proportions of the reagents employed in theprocesses can be varied over a relatively wide range, the particularamount to be employed being well within the ambit of those skilled inthe art, once armed with the present disclosures. For best results,however, it is important to maintain a ratio of less than one mole ofphase transfer agent per mole of Lewis acid. Preferably, the molar ratiois about 0.8 to 1.0, more preferably about 0.5 to 1.0, phase transferagent to Lewis acid. It should be noted that some phase transfer agentssold commercially are sold in an impure form. Such impurities usuallycomprise water or an alcohol species. Water and alcohol, as well asother impurities, will react adversely with the Lewis acid, therebylowering the amount of Lewis acid available for the process of thepresent invention. Accordingly, where the phase transfer agent addedcontains such impurities, the amount of Lewis acid should be increasedto account for these impurities. In such a situation, the ratio oftransfer agent to Lewis acid might be about 0.3 to 1.0. Such impureagent-containing mixtures are referred to herein as mixtures in an"impure form".

The processes can be carried out in any suitable vessel which providessufficient contacting between the Lewis acid, the phase transfer agentand the reactants. For simplicity, a stirred batch reactor can beemployed. Although stirring is recommended to provide efficient contactbetween reactants, it has been found that in the halogenated solvent, orin the unhalogenated solvent plus phase transfer agent and/or solvent,the Lewis acid is able to solubilize rather quickly, thereby obviatingthe need for stringent stirring requirements. The reaction vessel usedshould be resistant to the possible corrosive nature of the Lewis acid.Glass-lined vessels are suitable for this purpose, as well as othervessel materials well-known in the art.

The reagents may be added to the vessel in any order, although generallythe solvent, any phase transfer agent, and Lewis acid or protonic acid,are added first, followed by reactant addition

Ideally, the reaction is carried out at temperatures ranging from about-30° C. to about 50° C., preferably temperatures ranging from about -10°C. to about 30° C., and most preferably at temperatures ranging fromabout 0° C. to about 20° C.

The pressure at which the reaction is carried out is not critical. Ifthe reaction is carried out in a sealed vessel, autogenous pressure isacceptable, although higher or lower pressures, if desired, may beemployed. The reaction may also be carried out at atmospheric pressurein an open reaction vessel, in which case, the vessel is preferablyequipped with a moisture trap to prevent significant exposure of Lewisacid to moisture. The reaction may take place in an oxygen atmosphere oran inert atmosphere, as in the presence of a gas such as nitrogen, argonand the like, the type of atmosphere also not being critical.

Reaction time is generally rather short and is often dictated by thetype of equipment employed. Sufficient time should be provided, however,for thorough contacting of the reactants, the Lewis acid, the solvent,and any phase transfer employed. Generally, the reaction proceeds toequilibrium in about 1 to about 8 hours.

Preferably, the foregoing processes are carried out in the substantialabsence of elemental iodine (I₂). By "substantial absence", it is meantthat only a deminimus amount of iodine (such as, for example, less than1% by weight of I₂ based on the weight of the Lewis acid, if any, ispresent in the reaction medium. Preferably, the reaction medium isdevoid of any elemental iodine.

As those skilled in the art will recognize once armed with the presentdisclosure, by selecting from among the different reactants, differentformula [IV] compounds may be preferentially prepared, as illustrated inTable I below.

                                      TABLE I                                     __________________________________________________________________________                                    Preferential                                  Reactant 1     Reactant 2       Product                                       __________________________________________________________________________    5-isopropyl-meta-xylene and/or                                                               2-methyl-2-butene                                                                              Formula [IV]                                  5-isopropenyl-meta-xylene       wherein R.sup.1 = CH.sub.3                                                    and R.sup.2 = CH.sub.3                        5-isopropyl-meta-xylene and/or                                                               2-methylpropene (isobutylene)                                                                  Formula [IV] wherein                          5-isopropenyl-meta-xylene       R.sup.1 = H and R.sup.2 = CH.sub.3            5-isopropyl-meta-xylene and/or                                                               2-methyl-1-butene                                                                              Formula [IV]                                  5-isopropenyl-meta-xylene       wherein R.sup.1 = H                                                           and R.sup.2 = CH.sub.2 CH.sub.3               5-isopropyl-meta-xylene and/or                                                               3-methyl-2-pentene                                                                             Formula [IV]                                  5-isopropenyl-meta-xylene       wherein R.sup.1 = CH.sub.3                                                    and R.sup.2 = CH.sub.2 CH.sub.3               5-isopropyl-meta-xylene and/or                                                               2-methyl-2-pentene                                                                             Formula [IV]                                  5-isopropenyl-meta-xylene       wherein R.sup.1 = CH.sub.2 CH.sub.3                                           and R.sup.2 = CH.sub.3                        5-isopropyl-meta-xylene and/or                                                               3-methyl-3-hexene                                                                              Formula [IV]                                  5-isopropenyl-meta-xylene       wherein R.sup.1 = CH.sub.2 CH.sub.3                                           and R.sup.2 = CH.sub.2 CH.sub.3               meta-xylene    2,4-dichloro-2,3,4-trimethylpentane                                                            Formula [IV]                                                                  wherein R.sup.1 =  CH.sub.3                                                   and R.sup.2 = CH.sub.3                        __________________________________________________________________________

Product can be recovered from the reaction mixture by first quenchingthe reaction mixture in cold water or on crushed ice, preferably on ice,and then processing the mixture in the usual manner for Friedel-Craftsreactions to extract the desired compounds of Formula [IV]. Typically,following quenching and the resultant phase separation, the organiclayer is washed an additional time with water to aid in removal of theLewis acid. One or more additional washings can be carried out withdilute alkali solution to further aid Lewis acid removal. Still furtherpurification may be carried out, for example, using standard fractionaldistillation techniques, as well as other conventional extraction,distillation, crystallization, and chromotography techniques, and thelike. Suitable extraction and separation protocol is described, forexample, in George A. Olah, Friedel-Crafts And Related Reactions, Vols.1 and 2 (Interscience Publishers, John Wiley and Sons, 1964), thedisclosures of which are hereby incorporated herein by reference, in itsentirety.

Preferably the formula [IV] compounds are those compounds wherein:

R¹ is CH₃, and R² is CH₃, a compound which is1,1,2,3,3,4,6-heptamethylindane;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located cis to oneanother (that is, on the same side of the indane ring plane), a compoundwhich is cis-3-ethyl-1,1,2,3,4,6-hexamethylindane;

R¹ is CH₃, and R² is CH₂ CH₃, wherein R¹ and R² are located trans to oneanother (that is, on the opposite side of the indane ring plane), acompound which is trans-3-ethyl-1,1,2,3,4,6-hexamethylindane;

R¹ is H, and R² is CH₃, a compound which is1,1,3,3,4,6-hexamethylindane; and

R¹ is H, and R² is CH₂ CH₃, a compound which is3-ethyl-1,1,3,4,6-pentamethylindane.

The formula [IV] compounds may be employed alone, or in combination withone another, as compounds or compositions useful as reagents in thepreparation of the formula [I], [II] and [III] compounds. A particularlypreferred composition is one comprising, in combination, the formula[IV] compounds which are 1,1,2,3,3,4,6-heptamethylindane,cis-3-ethyl-1,1,2,3,4,6-hexamethylindane,trans-3-ethyl-1,1,2,3,4,6-hexamethylindane,1,1,3,3,4,6-hexamethylindane, and 3-ethyl-1,1,3,4,6-pentamethylindane.

The indane compounds of formula [IV] can then be formylated, that is,converted to compounds of formula [III] wherein R³ is CHO(carboxaldehydes), using conventional formylation technology.Specifically, to produce the formylated compounds of formula [III], theunformylated compounds of formula [IV] are preferably reacted withα,α-dichloromethyl methyl ether, in a solvent such as an organicsolvent, preferably a halogenated organic solvent such as, for example,anhydrous methylene chloride, in the presence of a Lewis acid. Othersuitable halogenated solvents are as discussed above in connection withthe preparation of the formula [IV] compounds. Such formylation methodsare well known in the art and are described, for example, in OrganicSynthesis, Collective Vol. 5, pp. 49-50 (John Wiley & Sons, 1973), thedisclosures of which are incorporated herein by reference, in theirentirety.

Further purification of the formylated compounds of formula [III] may becarried out, if desired, using, for example, standard fractionaldistillation techniques, as well as other conventional extraction,distillation, crystallization and chromotography techniques, and thelike.

In accordance with the preferable protocol, the novel aldoxime indanecompounds of formula [II] may then be prepared from the compounds offormula [III] using standard oximation methodology. The oximation may becarried out in a variety of different ways, according to well-knownmethodologies. Exemplary oximation techniques are set forth in Buchleret al., Survey of Organic Synthesis, pp. 956-958 (New York, John Wiley &Sons, Inc., 1970), and Wagner et al., Synthetic Organic Chemistry, pp.739-741 (New York, John Wiley & Sons, Inc., 1965), the disclosures ofeach of which are incorporated herein by reference, in their entirety.

Preferably, in accordance with standard oximation techniques, thecompounds of formula [III] are added to a solvent, such as a C₁ -C₄straight chain or branched monoalcohol such as methanol, ethanol,propanol and butanol. To this is then added hydroxylamine hydrochloridedissolved in water, and a base such as sodium hydroxide or the like, toproduce oxime compounds of formula [II]. Further purification of thealdoxime compounds of formula [II] may be carried out, if desired,using, for example, standard fractional distillation techniques, as wellas other conventional extraction, distillation, crystallization andchromotography techniques, and the like.

Further, in accordance with the preferable protocol, the novel nitrilecompounds of formula [I] may then be prepared from the aldoximecompounds of formula [II] using standard oxime dehydration methodology.Oxime dehydration may be accomplished in a variety of different waysaccording to conventional techniques. For examples of such techniquessee Buchler et al., Survey of Organic Synthesis, pp. 956-958 (New York,John Wiley & Sons, Inc., 1970), and Wagner et al., Synthetic OrganicChemistry, pp. 598-600 (New York, John Wiley & Sons, Inc., 1965), thedisclosures of each of which are incorporated herein by reference, intheir entirety.

Preferably, in accordance with standard oxime dehydration techniques,the compounds of formula [II] are reacted with acetic anhydride or thelike, followed by treatment with a base such as sodium hydroxide or thelike. The resultant nitrile indane compounds o: formula [I] may then beisolated, if desired, using standard isolation techniques, such as byconventional extraction, distillation, crystallization, andchromotography techniques, and the like.

Oximation and oxime dehydration processes are also described inChristenson et al., U.S. Pat. No. 4,483,786 and Kulka, U.S. Pat. No.3,910,853, the disclosures of each of which are hereby incorporatedherein by reference, in their entirety. Other processes for preparingnitrile compounds within the scope of the present invention will readilyapparent to those skilled in the art, once armed with the presentdisclosures, such as the techniques described in De Simone, U.S. Pat.No. 4,018,719, the disclosures of which are hereby incorporated hereinby reference, in their entirety.

The compounds of formulas [I] and [II] of the invention have highutility in the fragrance industry. These compounds may be used alone orin combination with one another or with one or more ingredients toprovide a musky fragrance composition.

For example, the formula [I] and [II] compounds of the invention may beused as olfactory components in anionic, cationic, nonionic andzwitterionic detergents, soaps, fabric softener compositions, fabricsoftener articles for use in clothes dryers, space odorants anddeodorants, perfumes, colognes, toilet water, toiletries, bathpreparations, deodorants, cosmetics, hand lotions, sunscreens, powders,as well as in other ways. The amount of the indane to be used inmodifying the olfactory properties of the compositions (that ismodifying, augmenting, enhancing, or improving the aroma of suchcompositions), will vary depending upon the particular use intended, aswill be readily apparent to those skilled in the art. Although they maybe present in major or minor amounts, preferably, because of thestrength of their odor, the compounds of the invention are generallyemployed as a minor ingredient, that is, in an amount of about 0.01% byweight of the fragrance composition up to about 50% by weight of thefragrance composition, preferably about 0.05% by weight up to about 30%by weight of the fragrance composition, and most preferably about 0.1%by weight up to about 5.0% by weight of the fragrance composition.Within these basic parameters, the olfactorily effective amount (thatis, the amount of the indane effective to modify, augment, enhance orimprove the aroma of a composition) will be well within the ambit of oneskilled in the art, once armed with the present disclosures.

The fragrance compositions of the invention may, if desired, contain avehicle or carrier (as used herein the term "carrier" shall beconsidered synonomous with the term "vehicle"). Such carriers includeliquids such as a non-toxic alcohol, a non-toxic glycol, or the like. Anexample of a non-toxic alcohol is ethyl alcohol. An example of anon-toxic glycol is 1,2-propylene glycol. Alternatively, the carrier canbe an absorbent solid such as a gum, e.g., gum arabic, xantham gum orguar gum, or components for encapsulating a composition such as gelatin,by means of coacervation or such as a urea formaldehyde polymer wherebya polymeric shell is formed around a liquid perfume oil center. Theamount of the vehicle or carrier will vary depending upon the particularuse intended, as will be readily apparent to those skilled in the art.However, the vehicle or carrier can generally be employed in an amountof about 5% by weight up to about 95% by weight of the fragrancecomposition.

The fragrance compositions may, if desired, contain other perfumerymaterials. Typical additional perfumery materials which may form part ofcompositions of the invention include: natural essential oils such aslemon oil, mandarin oil, clove leaf oil, petitgrain oil, cedar wood oil,patchouli oil, lavandin oil, neroli oil, ylang oil, rose absolute orjasmine absolute; natural resins such as labdanum resin or olibanumresin; single perfumery chemicals which ma be isolated from naturalsources or manufactures synthetically, as for example, alcohols such asgeraniol, nerol, citronellol, linalol, tetrahydrogeraniol,beta-phenylethyl alcohol, methyl phenyl carbinol, dimethyl benzylcarbinol, menthol or cedrol; acetates and other esters derived from suchalcohols; aldehydes such as citral, citronellal, hydroxycitronellal,lauric aldehyde, undecylenic aldehyde, cinnamaldehyde, amyl cinnamicaldehyde, vanillin or heliotropin; acetals derived from such aldehydes;ketones such as methyl hexyl ketone, the ionones and the methylionones;phenolic compounds such as eugenol and isoeugenol; synthetic musks suchas musk xylene, musk ketone and ethylene brassylate; and other materialscommonly employed in the art of perfumery. Typically at least five, andusually at least ten, of such materials will be present as components ofthe active ingredient. The amount of the additional perfumery materialwill vary depending upon the particular perfumery material employed anduse intended, as will be apparent to those skilled in the art.

Fragrance compositions and preparatory techniques are well known in theart, and are disclosed, for example, in "Soap, Perfumery and Cosmetics",by W. A. Poucher, 7th edition, published by Chapman & Hall (London)(1959); "Perfume and Flavour Chemicals", by S. Arctander, published bythe author (Montclair) (1959); and "Perfume and Flavour Materials ofNatural Origin", also by S. Arctander, self-published (Elizabeth, N.J.)(1960), the disclosures of each of which are hereby incorporated hereinby reference, in their entirety.

The present invention is further described in the following examples.These examples are not to be construed as limiting the scope of theappended claims.

In each example, results were analyzed on both polar and non-polar gaschromatography columns. All gas chromatography analyses were carried oncapillary columns using a weight percent internal standard method ofanalysis. Structural identifications were assigned based on acombination of GCMS fragmentation patterns and the spectroscopictechniques of NMR and IR compared to standards.

Example 1 describes the preparation of 1,1,2,3,3,4,6-heptamethylindaneand other indane compounds. Example 2 discusses the synthesis of5-formyl-1,1,2,3,3,4,6-heptamethylindane and other carboxaldehyde indanecompounds using the compounds of Example 1. Example discloses thepreparation of 1,1,2,3,3,4,6-heptamethylindane-5-aldoxime and1,1,2,3,3,4,6-heptamethylindane-5-nitrile using the5-formyl-1,1,2,3,3,4,6-heptamethylindane compound of Example 2.

EXAMPLES Example 1

A 100 ml four-necked round bottom flask equipped with an N₂ line,condenser, thermocouple-temperature controller, and addition funnel wascharged with CH₂ Cl₂ (9.79 g), and cooled to 15° C. with a dryice/isopropanol bath. To the flask was then added, with stirring,anhydrous AlCl₃ (0.874 g). While maintaining a temperature of 15° C., ahomogeneous mixture of 5-isopropyl-meta-xylene (21.7 g, 0.1466 moles)and 2-methyl-2-butene (20.53 g, 0.2932 moles) was added to the flaskover a period of about 30 minutes. The reaction was then allowed toproceed for about 2 additional hours at the same temperature. The flaskcontents were continuously stirred throughout the reaction.

The reaction was then quenched with cold deionized water (10 ml), andthe resultant product further treated with 10% aqueous NaHCO₃ andextracted with CH₂ Cl₂. After drying with anhydrous Na₂ SO₄, the organicsolution was rotoevaporated to give about 30 g of crude productcontaining about 50 weight percent of 1,1,2,3,3,4,6-heptamethylindane,in addition to other indane compounds.

Example 2

To a 1 l three-necked flask equipped with a reflux condenser, a stirrer,and a dropping funnel, was charged 21.6 g of the crude productcontaining about 50 weight percent 1,1,2,3,3,4,6-heptamethylindane fromExample 1, and 115 ml anhydrous CH₂ Cl₂. The solution was then cooled inan ice bath, and 31.61 g (18.3 ml, 0.166 moles) TiCl₄ was added over aperiod of about 3 minutes. While the solution is stirred and cooled,9.53 g (7.5 ml, 0.083 moles) α,α-dichloromethyl methyl ether was addeddropwise over a 10 minute period, while maintaining a temperature ofabout 0° to about 5° C. After the addition is complete, the mixture isstirred for about 20 minutes in an ice bath, for about 30 minuteswithout cooling, and finally for about 15 minutes at 35° C.

The reaction mixture was then poured into a separatory funnel containingabout 0.2 kg of crushed ice and shaken thoroughly. The organic layer isseparated, and the aqueous solution is extracted with two 50 ml portionsof methylene chloride. The combined organic solution is washed threetimes with 50 ml portions of water. A crystal of hydroquinone is addedto the methylene chloride solution which is then dried over anhydroussodium sulfate. After evaporation of the solvent, the residue isdistilled to give 21.82 g of crude product containing 53.5% of5-formyl-1,1,2,3,3,4,6-heptamethylindane, or further distilled usingconventional techniques to yield a more purified indane productcontaining 77.0% of 5-formyl-1,1,2,3,3,4,6-heptamethylindane, 3.2% ofcis-5-formyl-3-ethyl-1,1,2,3,4,6-hexamethylindane, 5.5% oftrans-5-formyl-3-ethyl-1,1,2,3,4,6-hexamethylindane, 1.2% of5-formyl-1,1,3,3,4,6-hexamethylindane, and 4.8% of5-formyl-3-ethyl-1,1,3,4,6-pentamethylindane.

Example 3

The more purified indane product of Example 2 was distilled usingstandard fractional distillation techniques to obtain the5-formyl-1,1,2,3,3,4,6-heptamethylindane compound.

A 250 ml three-necked flask, equipped with a condenser, thermometer, andaddition funnel, was then charged with ethanol (80 ml) and5-formyl-1,1,2,3,3,4,6-heptamethylindane (19.4 g, 80 mmole).Hydroxylamine hydrochloride solution (8.25 g, 120 mmole in 20 ml water)was added in one aliquot, and stirred at about 60° C. for about 30minutes. The reaction mixture was neutralized at about 60° C. with 10%aqueous sodium hydroxide (47 ml), and stirred at about 64° C. for aboutone hour. The mixture was then chilled to about 5° C., and the resultantwhite solid was filtered and washed with water in a Buchner funnel toprovide the oxime compound 1,1,2,3,3,4,6-heptamethylindane-5-aldoxime(19.2 g).

A 100 ml round bottomed flask equipped with a condenser was charged withthe oxime compound 1,1,2,3,3,4,6-heptamethylindane-5-aldoxime (19.2 g)and acetic anhydride (40 ml). The reaction mixture was refluxed forabout 3 hours. The reaction was then cooled to room temperature and themixture poured into 10% aqueous sodium hydroxide (175 ml). The aqueouslayer was extracted with dichloromethane (4 times with 20 ml). Theorganic extract was then washed with water (20 ml) and brine (20 ml),and dried over anhydrous sodium sulfate. Solvent was removed by rotaryevaporation to provide crude nitrile (17.9 g, 83% purity). The productwas distilled (0.5 mm, 130°-132° C.) and subsequently recrystallizedfrom ethanol (mp=83°-85° C.), providing1,1,2,3,3,4,6-heptamethylindane-5-nitrile.

Various modifications of the invention, in addition to those shown anddescribed herein, will be apparent to those skilled in the art from theforegoing description. Such modifications are also intended to fallwithin the scope of the appended claims.

What is claimed is:
 1. A compound of the formula [I] ##STR13## whereinR¹ is H, CH₃, and CH₂ CH₃, andR² is CH₃, and CH₂ CH₃.
 2. A compound ofclaim 1 wherein R¹ is H or CH₃, and R² is CH₃.
 3. A compound of claim 1which is 1,1,2,3,3,4,6-heptamethylindane-5-nitrile.
 4. A compound ofclaim 1 which is cis-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile. 5.A compound of claim 1 which istrans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile.
 6. A compound ofclaim 1 which is 1,1,3,3,4,6-hexamethylindane-5-nitrile.
 7. A compoundof claim 1 which is 3-ethyl-,1,1,3,4,6-pentamethylindane-5-nitrile.
 8. Acomposition comprising at least two compounds of the formula [I]##STR14## wherein R¹ is H, CH₃, and CH₂ CH₃, andR² is CH₃, and CH₂ CH₃.9. A composition of claim 8 wherein the formula [I] compounds comprise,in combination, compounds which are1,1,2,3,3,4,6-heptamethylindane-5-nitrile,cis-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile,trans-3-ethyl-1,1,2,3,4,6-hexamethylindane-5-nitrile,1,1,3,3,4,6-hexamethylindane-5-nitrile, and3-ethyl-1,1,3,4,6-pentamethylindane-5-nitrile.
 10. A fragrancecomposition comprising a compound of claim 1 in combination with atleast one of a carrier and additional perfumery material.
 11. Afragrance composition comprising a compound of claim 3 in combinationwith at least one of a carrier and additional perfumery material.
 12. Afragrance composition comprising a composition of claim 8 in combinationwith at least one of a carrier and additional perfumery material.
 13. Afragrance composition comprising a composition of claim 9 in combinationwith at least one of a carrier and additional perfumery material.
 14. Amethod of modifying the olfactory properties of a composition comprisingadding thereto an olfactorily effective amount of a compound of claim 1.15. A method of modifying the olfactory properties of a compositioncomprising adding thereto an olfactorily effective amount of a compoundof claim
 3. 16. A method of modifying the olfactory properties of acomposition comprising adding thereto an olfactorily effective amount ofa composition of claim
 8. 17. A method of modifying the olfactoryproperties of a composition comprising adding thereto an olfactorilyeffective amount of a composition of claim 9.